Secondary isopropyl amine derivatives of polyoxyalkylene diamines and triamines

ABSTRACT

Secondary isopropylamine terminated polyoxyethylene and/or polyoxypropylene diamines or triamines are formed in a one-step reaction when a polyoxyethylene and/or polyoxypropylene primary diamine or triamine is hydrogenated with hydrogen in the presence of a hydrogenation catalyst, hydrogen and acetone. The secondary isopropylamine terminated polyoxyethylene and/or polyoxypropylene primary diamines or triamines are useful as curing agents for epoxy resins.

This is a division, of application Ser. No. 07/135,798, filed Dec. 21,1987, aband.

BACKGROUND OF THE INVENTION

1. Technical Field of the Invention

This invention relates to secondary isopropyl amine derivatives ofpolyoxyalkylene primary diamines and triamines. More particularly, thisinvention relates to secondary isopropyl amine derivatives ofpolyoxyethylene and/or polyoxypropylene primary diamines or triaminesprepared by the reaction of a polyoxyethylene and/or polyoxypropyleneprimary diamine or triamine with acetone in the presence of ahydrogenation catalyst and hydrogen. Still more particularly, thisinvention relates to a method wherein a polyoxyethylene and/orpolyoxypropylene primary diamine or triamine having a molecular weightof about 200 to about 400 is reacted with acetone in the presence ofhydrogen and a hydrogenation catalyst to provide a secondary isopropylamine terminated polyoxyethylene and/or polyoxypropylene reactionproduct and to the use of such products as curing agents for epoxyresins.

2. Prior Art

Speranza et al. U.S. Pat. No. 3,110,732 is directed to a method forpreparing primary amine derivatives of polyoxyalkylene glycol by athree-step process wherein an alkanolamine having a primary amine groupis reacted with a higher carbonyl compound such as methylethyl ketone,isobutyraldehyde, etc., to form a condensation product which may beeither a Schiff base or an oxazolidine which is thereafter alkoxylatedwith an alkylene oxide to provide an adduct followed by hydrolysis ofthe adduct to form a primary amine basic polyether composition.

Speranza U.S. Pat. No. 3,364,239 is directed to secondary aminopolyalkoxy monoalkanols which are prepared by reacting a primary aminopolyalkoxy alkanol with a higher carbonyl compound such as methylethylketone, butyraldehyde, etc., to form a Schiff base reaction productwhich is thereafter hydrogenated in the presence of a hydrogenationcatalyst at an elevated temperature and pressure to provide thesecondary amino polyalkoxy monoalkanol.

Malz, Jr. et al. U.S. Pat. No. 4,607,104 is directed to a processwherein 2,2,6,6-tetraalkyl-4-piperidylamines are prepared by reacting anamine with 2,2,6,6-tetraalkyl-4-piperidone in the presence of water, analiphatic alcohol or aliphatic glycol and a platinum, nickel or cobaltcatalyst.

BACKGROUND OF THE PRESENT INVENTION

As exemplified by the Speranza and Speranza et al. patents, it is knownthat when a higher ketone such as methylethyl ketone is reacted with aprimary amine the reaction product is a Schiff base or an oxazolidine.This Schiff base may thereafter be hydrogenated to provide a secondaryamino polyalkoxy alkanol. Thus, a two-step reaction is required.Moreover, acetone is not a suitable ketone for the use in a two-stepreaction of this nature because of its boiling point.

It has now been surprisingly discovered that when a polyoxyethyleneand/or polyoxypropylene primary diamine or triamine is reacted withacetone in the presence of a hydrogenation catalyst and hydrogen,secondary isopropylamine terminated polyoxyethylene and/orpolyoxypropylene primary diamines and triamines can be formed in onestep. The polyoxyethylene and/or polyoxypropylene primary diamine ortriamine should have a molecular weight within the range of about 200 toabout 400, the ratio of acetone to primary diamine or triamine startingmaterial should be within the range of about 1.5 to about 3 moleequivalents of acetone per mole of primary amine group present in theprimary diamine or triamine and the reaction should be conducted at atemperature within the range of about 50° to about 200° C. and apressure within the range of about 100 to about 4000 psig., including ahydrogen partial pressure of about 50 to about 2,500 psi.

The secondary isopropylamine derivatives that are prepared by theprocess have been found to be useful as flexible curing agents for epoxyresins.

SUMMARY OF THE INVENTION

The starting materials for the present invention are a polyoxypropyleneand/or polyoxyethylene primary diamine or triamine having a molecularweight of 200 to about 400, acetone, hydrogen and a hydrogenationcatalyst.

The Polyoxyalkylene Primary Diamine and Triamine Starting Materials

The polyoxyalkylene polyamine starting materials for the presentinvention are selected from the group consisting of polyoxypropylenediamines and triamines, and polyoxyethylene diamines, andpolyoxyalkylene diamines and triamines containing mixtures of bothethylene oxide and propylene oxide and, preferably, mixtures of fromabout 5 to about 40 wt. % of ethylene oxide with, correspondingly, fromabout 95 to 60 wt. % of propylene oxide. Where mixed propyleneoxide/ethylene oxide polyols are employed, the ethylene oxide andpropylene oxide may be premixed prior to reaction to form a heterocopolymer, or the ethylene oxide and the propylene oxide may besequentially added to the ethoxylation kettle to form blockoxypropylene/oxyethylene copolymers.

The polyoxyalkylene primary polyamine starting material are selectedfrom the group consisting of polyoxyalkylene primary diamines andtriamines having the formula: ##STR1##

Wherein R is the nucleus of an oxyalkylation-susceptible polyhydricalcohol containing 2 to 12 carbon atoms and 2 or 3 hydroxyl groups, andR' is hydrogen or methyl, n is a number sufficient to impart a molecularweight of about 200 to about 400 to the molecule, and m is an integerhaving a value of 2 to 3.

One group of appropriate polyoxyalkylene diamines that may be used arethose that are sold by the Texaco Chemical Company as Jeffamine®D-series products having the formula: ##STR2## Wherein R' independentlyrepresents hydrogen or methyl and x is a number having an average valueof about 1 to about 6.

Representative products having this structural formula includepolyoxypropylene diamines (wherein R' is methyl) having an averagemolecular weight of about 230 wherein the value of x is between 2 and 3(Jeffamine® D-230 amine), and polyoxypropylene diamines having anaverage molecular weight of about 400 wherein x has a value betweenabout 5 and 6 (Jeffamine® D-400 amine).

As other examples, the primary amine starting material may betriethylene glycol diamine (sold commercially by Texaco Chemical Companyas Jeffamine® EDR-148) and tetraethylene glycol diamine (sold by TexacoChemical Company commercially as Jeffamine® EDR-192).

An example of appropriate polyoxypropylene triamines that may be used asa starting material for the present invention include triamines sold byTexaco Chemical Company as Jeffamine® T-series products having theformula: ##STR3## Wherein A represents the nucleus of an oxyalkylationsusceptible trihydric alcohol containing about 3 to about 6 carbonatoms, w, y and z are numbers and the average value of the sum of w+y+zis sufficient to impart an average molecular weight of not more thanabout 400 to the molecule.

An example of such a product is a commercial product having an averagemolecular weight of about 400 wherein A represents a trimethylol propanenucleus (Jeffamine® T-403 amine).

Acetone

Secondary isopropylamine derivatives of the primary diamine and triaminestarting materials are prepared by reacting the diamine or triaminestarting material with acetone.

It is important that the acetone be utilized in the right proportions ifthe desired products are to be obtained with good yield and selectivity.Thus, from about 1.5 to about 3 mole equivalents of acetone should beused for each mole equivalent of primary amine group in the primaryamine starting material. For example, if the starting material is apolyoxyalkylene primary diamine, from about 3 to about 6 moles ofacetone should be used per mole of diamine starting material. For atriamine, the molar ratio would be within the range of about 4.5:1 toabout 9:1.

Ketones other than acetone or aldehydes do not give equivalent results.Thus, either a loss of yield and/or selectivity will be experienced whenthe reaction parameters of the present invention are used with otherketones or with aldehydes.

Hydrogen

The acetone is reacted with the polyoxyalkylene primary diamine ortriamine starting material in the presence of added hydrogen. Thereaction is conducted at an elevated temperature and pressure. Normally,the reactants can be pressured at a desired pressure with hydrogen andhydrogen may be used thereafter to maintain the pressure so that thereaction pressure and the hydrogen partial pressure will be essentiallythe same. The reaction pressure should be within the range of about 100to about 4000 psi., including a hydrogen partial pressure of about 50 toabout 2,500.

The Hydrogenation Catalyst

Any suitable hydrogenation catalyst may be used such as a catalystcomprising one or more of the metals of group VIIIB of the PeriodicTable, such as iron, cobalt, nickel, ruthenium, rhodium, palladium,platinum, mixed with one or more metals of group VIB of the PeriodicTable such as chromium, molybdenum or tungsten. A promoter from group IBof the Periodic Table, such as copper, may also be included. As anexample, a catalyst may be used comprising from about 60 to 85 molepercent of nickel, about 14 to 37 mole percent of copper and about 1 toabout 5 mole percent of chromium (as chromia), such as a catalystdisclosed in Moss U.S. Pat. No. 3,151,112 or Yeaky U.S. Pat. No.3,654,370. As another example, a catalyst of the type disclosed inBoettger et al. U.S. Pat. No. 4,014,933 may be used containing fromabout 70 to about 95 wt. % of a mixture of cobalt and nickel and fromabout 5 to about 30 wt. % of iron. As another example, a catalyst of thetype disclosed in Habermann U.S. Pat. No. 4,152,353 may be used, such asa catalyst comprising nickel, copper and a third component which may beiron, zinc, zirconium or a mixture thereof, e.g., a catalyst containingfrom about 20 to about 49 wt. % of nickel, about 36 to about 79 wt. % ofcopper and about 1 to about 15 wt. % of iron, zinc, zirconium or amixture thereof.

Reaction Conditions

As indicated above, the reaction should be conducted at a temperaturewithin the range of about 50° to about 200° C. and a pressure within therange of about 100 to about 4,000 psig., including a hydrogen partialpressure of about 50 to about 2,500 psi.

The reaction may be conducted on a batch base using powderedhydrogenation catalysts or on a continuous basis utilizing a pelletedhydrogenation catalyst.

When the reaction is conducted on a batch basis, reaction time shouldpreferably be within the range of about 1 to about 12 hours. When thereaction is conducted on a continuous basis, wherein the primary aminestarting material and the acetone are continuously passed over a bed ofpelleted hydrogenation catalysts, the feed rate for the primary amineshould preferably be within the range of about 0.5 to about 3 w/hr/w forthe primary amine and about 0.5 to about 3 w/hr/w for the acetone.

USE OF ISOPROPYL SECONDARY AMINES AS FLEXIBLE CURING AGENTS FOR EPOXYRESINS

It has been discovered in accordance with the present invention that thepolyoxyethylene and/or polyoxypropylene primary diamines and triaminesare useful as flexible curing agents for epoxy resins.

UTILITY OF SECONDARY ISOPROPYL AMINES AS EPOXY CURING AGENTS

A particular utility for which the secondary poly (secondary isopropylamino) polyoxyethylene and/or polyoxypropylene diamines and triamines ofthe present invention are well suited is found when they are used ascuring agents for 1,2-epoxy resins.

It is known to use amines such as aliphatic or aromatic amines forcuring 1,2-epoxy resins as shown, for example, by Waddill U.S. Pat. No.4,139,524 and Marquis et al. U.S. Pat. No. 4,162,358. See also, thetextbook "Handbook of Epoxy Resins" by H. Lee and K. Neville,McGraw-Hill Book Company, 1967.

Generally the vicinal epoxide compositions that can be cured using thecuring agents of this invention are organic materials having an averageof more than one reactive 1,2-epoxide group. These polyepoxide materialscan be monomeric or polymeric, saturated or unsaturated, aliphatic,cycloaliphatic, aromatic or heterocyclic, and may be substituted ifdesired with other substituents besides the epoxy groups, e.g., hydroxylgroups, ether radicals, halogenated phenyl groups and the like.

The most widely used epoxy resins are diglycidyl ethers of bisphenol A:##STR4## where n equals an integer of up to about 10 to 20.

However, these epoxides are representative of the broader class ofepoxide compounds that are useful in making epoxy resins.

A widely used class of polyepoxides that can be cured according to thepractice of the present invention includes the resinous epoxy polyethersobtained by reacting an epihalohydrin, such as epichlorohydrin, and thelike, with either a polyhydric phenol or a polyhydric alcohol. Anillustrative, but by no means exhaustive, listing of suitable dihydricphenols includes 4,4'-isopropylidene bisphenol,2,4'-dihydroxydiphenylethylmethane,3,3'-dihydroxydiphenyldiethylmethane,3,4'-dihydroxydiphenylmethylpropylmethane,2,3'-dihydroxydiphenylethylphenylmethane, 4,4'-dihydroxydiphenylmethane,4,4'-dihydroxydiphenylbutylphenylmethane,2,2'-dihydroxydiphenylditolylmethane,4,4'-dihydroxydiphenyltolylmethyl-methane and the like. Other polyhydricphenols which may also be co-reacted with an epihalohydrin to providethese epoxy polyethers are such compounds as resorcinol, hydroquinone,substituted hydroquinones, e.g., tertbutylhydroquinone, and the like.

Among the polyhydric alcohols that can be co-reacted with anepihalohydrin to provide the resinous epoxy polyethers are suchcompounds as ethylene glycol, propylene glycol, butylene glycols,pentane diols, bis(4-hydroxycyclohexyl)dimethylmethane,1,4-dimethylolbenzene, glycerol, 1,2,6-hexanetriol, trimethylolpropane,mannitol, sorbitol, erythritol, pentaerythritol, their dimers, trimersand higher polymers, e.g., polyethylene glycols, polypropylene glycols,triglycerol, dipentaerythritol and the like, polyallyl alcohol,polyhydric thioethers, such as 2,2'-, 3,3'-tetrahydroxydipropylsulfideand the like, mercapto alcohols such as α-monothioglycerol,α,α'-dithioglycerol, and the like, polyhydric alcohol partial esters,such as monostearin, pentaerythritol monoacetate, and the like, andhalogenated polyhydric alcohols such as the monochlorohydrins ofglycerol, sorbitol, pentaerythritol and the like.

Another class of polymeric polyepoxides that can be cured by means ofthe above-described curing agents includes the epoxy novolac resinsobtained by reacting, preferably, in the presence of a basic catalyst,e.g., sodium or potassium hydroxide, an epihalohydrin, such asepichlorohydrin, with the resinous condensate of an aldehyde, e.g.,formaldehyde, and either a monohydric phenol, e.g., phenol itself, or apolyhydric phenol. Further details concerning the nature and preparationof these epoxy novolac resins can be obtained in Lee, H. and Neville,K., "Handbook of Epoxy Resins".

It will be appreciated by those skilled in the art that the polyepoxidecompositions that can be cured according to the practice of the presentinvention are not limited to the above described polyepoxides, but thatthese polyepoxides are to be considered merely as being representativeof the class of polyepoxides as a whole.

The amount of curing agent that is employed in curing polyepoxidecompositions will depend on the amine equivalent weight of the curingagent employed. The total number of equivalents of amine group ispreferably from about 0.8 to about 1.2 times the number of epoxideequivalents present in the curable epoxy resin composition with astoichiometric amount being most preferred.

Various conventionally employed additives can be admixed with thesepolyepoxide-containing compositions prior to final cure. For example, incertain instances it may be desired to add minor amounts of otherco-catalysts, or hardeners, along with the curing agent system hereindescribed. Conventional pigments, dyes, fillers, flame retarding agentsand other compatible natural and synthetic resins can also be added.Furthermore, known solvents for the polyepoxide materials such asacetone, methyl ethyl ketone, toluene, benzene, xylene, dioxane, methylisobutyl ketone, dimethylformamide, ethylene glycol monoethyl etheracetate, and the like, can be used if desired, or where necessary.

cl WORKING EXAMPLES--BATCH EXPERIMENTS

Preparation of N-Isopropyl Diamines and Triamines Example 1(6245-49)--Hydrogenation of Triethylene Glycol Diamine (JeffamineEDR-148 Amine) with Acetone (2:3 Ratio)

To a 1-liter stirred autoclave was charged EDR-148 (296 g, 2 moles),acetone (174 g, 3 moles) and a nickel, copper, chromia catalystcontaining about 75 mole % nickel, 23 mole % copper and 2 mole %chromium (25 g). The autoclave was sealed and flushed twice withhydrogen. The reactor was pressured to 1000 psi of hydrogen and heatedto 180° C. Then, the pressure was raised to 2500 psi and maintained atthis pressure with incremental addition of hydrogen until no pressureuptake was noticed. The reaction time was about 5 hrs. The mixture wasallowed to cool to room temperature. The catalyst was recovered throughfiltration. The filtrate was distilled to give N-isopropyl triethyleneglycol diamine (¹) (approx. 90% purity, b.p. 120°-129° C./12 mm Hg, 200g) and N,N'-diisopropyl triethylene glycol diamine, (²) (b.p. 134°-140°C./11 mm Hg, 66.2 g). ##STR5##

Example 2 (6245-81) --Hydrogenation of Triethylene Glycol Triamine(Jeffamine EDR-148 Amine) and Acetone Mixture (2:4.1 Mole Ratio)

The experimental procedures of the above example were followed. Themixture of EDR-148 (296 g, 2 moles) and acetone (240 g, 4.1 moles) washydrogenated. The reaction conditions were 2900 psi and 180° C. forabout 5 hours using 5 g of the nickel, copper, chromia catalyst ofExample 1. After filtration, the crude product contained total amine7.36 meq/g and secondary amine 6.65 meq/g, indicating a high conversionof the EDR-148/acetone reaction.

Example 3 (6245-89)--Hydrogenation of Triethylene Glycol Diamine(Jeffamine EDR-148 Amine) with Acetone (1.0:1.1 Ratio)

The procedures of Example 1 were repeated, except using EDR-148 (296 g,2 moles), acetone 9128 g, 2.2 moles) and 25 g of the nickel, copper,chromia catalyst of Example 1. The reaction conditions were 2900 psi H₂and 180° for about 6 hours. The catalyst was removed by filtration. Theamine content of 3.97 meq/g (total amine) and 2.95 meq/g (secondaryamine) was found in the crude product.

Example 4 (6250-52)--Hydrogenation of Triethylene Glycol Diamine(Jeffamine EDR-148 Amine) with Acetone (2:4.1 Mole Ratio)

The experimental procedures were repeated except using EDR-148 (296 g, 2moles), acetone (240 g, 4.1 moles) and 5% pd on carbon 92.0 g). Withreaction conditions of 1500 psi H₂ pressure, 80° C. and ca. 6 hours.After filtration, the filtrate was subjected to vacuum to remove lightmaterials. The product was analyzed by amine titration and found to havethe content of total amine 7.40 meq/g and secondary amine 7.08 meq/g,which indicated high conversion of EDR-148.

Example 5 (6250-1) --Hydrogenation of bis-Aminoethylether (BAEE) -Acetone Mixture (1:2 Ratio)

To a 1-liter stirred autoclave was charged bisaminoethylether (BAEE)(208 g, 2.0 mole), acetone (232 g, 4.0 moles) and 25 grams of thenickel, copper, chromia catalyst of Example 1. The reactor was flushedtwice with hydrogen and pressured to 1500 psi. After heating to 180° C.,the hydrogen pressure was raised to 3000 psi and held for 3 hours. Thecatalyst was recovered by filtration. The filtrate was distilled twiceunder vacuum to give N-isopropyl bisaminoethylether (58.3 g, bp 91°-94°C./13 mm Hg).sup.(3) and N,N'-diisopropyl bis-aminoethylether (128.2 g,97°-100° C./10 mm Hg).sup.(4). These compounds were confirmed by H-nmr.##STR6##

EXAMPLE 6 (6250-40)--Hydrogenation of Tetraethylene Glycol Diamine(Jeffamine EDR-192 Amine) and Acetone (1:2.5 Mole Ratio)

The experimental procedures of Example 1 were repeated, except chargingEDR-192 (409 g, 94%, approx. 2 moles), acetone (248 g, 4.9 moles) and 25grams of the nickel, copper, chromia catalyst of Example 1. The reactionconditions were 3000 psi H₂ pressure, 180° C. and 4 hrs. The catalystwas recovered by filtration. The product was distilled to give 312 g ofN,N'-diisopropyl triethylene glycol diamine (b.p. 148°-157° C./2.5-3.9mm Hg). This major product was confirmed by N-nmr to be ##STR7##

EXAMPLE 7 (6250-33)--Hydrogenation of a Polyoxypropylene Diamine havingan Average Molecular Weight of 230 (Jeffamine D-230 Amine) with Acetone(1:4 Mole Ratio)

The experimental procedures were repeated with the mixture ofJEFFAMINE®D-230 (299 g, 1.3 moles), acetone (307 g, 5.2 moles) and 25grams of the nickel, copper, chromia catalyst of Example 1. Theconditions were 3000 psi H₂ pressure, 180° C. and ca. 3.5 hours. Thecatalyst was recovered by filtration. The light materials were removedby cold-trap under vacuum. The crude product was light colored liquidwith amine contents of 6.53 meg/g (calc. 6.4 meg/g) for total amine and4.03 meg/g for secondary amine. (The product was obtained in the amountof 336g).

Example 8 (6250-65)--Hydrogenation of a Polyoxypropylene Diamine havingan Average Molecular Weight of 230 (Jeffamine D-230 Amine) and Acetone(1:4 Mole Ratio)

The previous reaction was repeated, except using Pd 5% on c as catalyst.The reaction conditions were 1500 psi H₂ pressure, 80° C. and 14 hours.The crude product was filtered and stripped of the light material. Thefinal product was light colored liquid with analyses of 6.16 meg/g totalamine (6.37 meg/g calc.) and 6.13 meg/g secondary amine. The highcontent of secondary amine indicated the high conversion of primary tosecondary amine. (The total product recovery was 377 g).

Example 9 (6250-3)--Hydrogenation of a Polyoxypropylene Diamine havingan Average Molecular Weight of 2000 (Jeffamine D-2000 Amine) and Acetone(1:6 Mole Ratio)

The reaction procedures of Example 1 were employed, except usingJEFFAMINE D-2000 (500 g, 0.25 moles), acetone (87 g, 1.5 moles) andNi-2715 (25 g). The conditions were 3000 psi H₂ pressure, 180° C. and 5hours. After filtration and vacuum strip-off light material, a liquidmaterial (456 g) was recovered. The analysis indicated the contents ofprimary amine 0.65 meg/g and secondary amine 0.29 meg/g.

Example 10 (6250-2)--Hydrogenation of Polyoxypropylene Diamine having anAverage Molecular Weight of about 400 (Jeffamine D-400 Amine) andAcetone (1:4 Mole Ratio) A similar experimental procedure was usedexcept employing JEFFAMINE D-400 (400 g, 1.0 mole), acetone (232 g, 4.0meg/g) and 25 grams of the nickel, copper, chromia catalyst ofExample 1. The conditions were 3000 psi H₂ pressure, 180° C. and approx.5 hours. After filtration and light material removal, the product hadamine content of 1.8 meg/g for primary and 2.1 meg/g for secondaryamine. Example 11 (6250-5)--Hydrogenation of Triethylene Glycol Diamine(Jeffamine EDR-148 Amine) with Methyl Ethyl Ketone (3:1 Mole Ratio)

The experimental procedures were conducted in similar fashion toExample 1. The mixtures of EDR-148 (296 g, 2.0 moles) methyl ethylketone (216 g, 3.0 moles) and nickel, copper, chromia catalyst (25 g)were hydrogenated under conditions of 3000 psi H₂, 180° C. for ca. 4hours. After filtration, the product was isolated by vacuumdistillation: N-(2-butyl)triethylene glycol diamine (ca. b.p. 136°C./4.6 mm Hg, 228 g).sup.(6), amine content: 9.85 meg/g total and 5.05meg/g primary. ##STR8## N,N'-di(2-butyl)triethylene glycol diamine (7)(b.p. ca. 142° C./4.0 mm Hg 87 g). Amine content: 7.70 meg/g total and0.09 meg/g primary. Both compounds (6) and (7) were confirmed by H-nmr.

Example 12 (6285-9)--Hydrogenation of Polyoxypropylene Triamine havingan Average Molecular Weight of 400 (Jeffamine T-403 Amine) with Acetone(1:1 Mole Ratio)

To a 1 liter autoclave was charged T-403 (465 g, about 1.0M), acetone(58 g, 1.0M) and Pd/c 1% (2.0 g). The autoclave was sealed and purgedwith hydrogen. The reaction was then pressured to 1000 psi with hydrogenand heated to 80° C. During the process, the pressure uptake wasobserved. Additional hydrogen was added to maintain 1500 psi for 7hours. The reactor was allowed to cool to room temperature. The productmixture was filtered. The filtrate was subjected to vacuum to removelight material, including water, acetone and isopropanol. The productmixture was analyzed: 5.46 meg/g for primary amine and 0.76 meg/g forsecondary amine. It is estimated that about 12% of amine is secondaryamine in the JEFFAMINE T-403 amine reaction product.

Example 13 (6285-10)--Hydrogenation of Polyoxypropylene Triamine havingan Average Molecular Weight of 400 (Jeffamine T-403 Amine) with Acetone(1:2 Mole Ratio)

The same procedures of Example 12 were repeated except using T-403 (465g, 1M) and acetone (116 g, 2M) and pd/c 1% (2 g). The reactionconditions were 1500 psi H₂ and 9 hours at 80° C. The product wasfiltered and stripped of solvent and by-product. The analyses of finalproduct indicated 5.05 meg/g for primary amine and 1.12 meg/g for 2°-amine. The secondary amine content was estimated to be about 18%.

Example 14 (6285-11)--Hydrogenation of Polyoxypropylene Triamine havingan Average Molecular Weight of 400 (Jeffamine T-403 Amine) with Acetone(1:3 Mole Ratio)

Following the same procedures described above. The product contained4.72 meg/g 1° -amine and 1.37 meg/g 2° -amine. The 2° -amine was about22%.

Example 15 (6285-83)--Hydrogenation of Polyoxypropylene Triamine havingan Average Molecular Weight of 400 (Jeffamine T-403 Amine) with Acetone(1:6 Mole Ratio)

The similar procedures of Example 12 were used except charging T-403(418 g, 0.9M), acetone (314 g, 5.4M) and pd/c 1% (2 g). The reactionconditions were 2000 psi H₂ -pressure, 120° C. for ca. 14 hours. Afterfiltration and removal of by-products, the final product contained ca.84% secondary amine.

Example 20 (6310-100)--Continuous Reaction of Ethylene Diamine andAcetone with Hydrogen

Ethylenediamine (120 g, 2 moles), acetone (348 g 6.0 moles) and 25 gramsof the nickel, copper chromia catalyst of Example 1 were charged to a 1liter autoclave. The autoclave was sealed and flushed with hydrogen andthen pressured with hydrogen to 1,000 psig. While heating to 130° C.,the pressure was increased to 3,000 psig and held at 3,000 psig withincremental supply of hydrogen from a surge tank until no pressureuptake was observed. The pressure uptake ceased after about 8 hours. Thereactor was cooled to room temperature and 450 g of liquid product wasrecovered after filtration. Analysis (G.C.) indicated that there were nomajor products such as N,N'-diisopropyl ethylenediamine or N-isopropylethylenediamine.

Discussion

Note that in Example 1 wherein triethylene glycol diamine was reactedwith acetone in the molar ratio of 2 moles of diamine and 3 moles ofacetone that both the N,N'-diisopropyl triethylene glycol diamine andthe N-isopropyl triethylene glycol diamine were formed whereas inExample 2 wherein the molar ratio of the same reactants was 2:4.1, morethan 90% of the reaction product constituted the N,N'-diisopropyltriethylene glycol diamine. In Example 3 wherein the molar ratio forthese reactants is 1.0:1.1, note that only about 74% of the diisopropylamine derivative was obtained.

Good results were obtained in Example 4 at a 2:4.1 molar ratio oftriethylene glycol diamine to acetone and this was also the case inExample 5 wherein bisaminoethylether was reacted with acetone in a 1:2molar ratio. In Example 6, the reaction of tetraethylene glycol diaminewith acetone in the molar ratio of 1:2.5 resulted in a substantiallyquantitative conversion of the feedstock to N,N'-diisopropyl triethyleneglycol diamine. However, in Example 7 when a polyoxypropylene diaminewas reacted with acetone in the molar ratio of 1:4, only about 62% ofthe secondary amine was found in the reaction product whereas in Example8 wherein the molar ratio of the reactants was 1:4, substantially all ofthe reaction product was the diisopropyl amine derivative. In Example 9when the polyoxypropylene diamine having a molecular weight of 2000 wasused, unsatisfactory results were obtained in that only about 30% of thereaction product was secondary amine. This is also true in Example 10wherein a polyoxypropylene diamine having a molecular weight of about400 was reacted with acetone in the ratio 1:4. Unsatisfactory resultswere also obtained in Example 11 wherein triethylene glycol diamine wasreacted with a methyl ethyl ketone.

In Example 12 wherein a polyoxypropylene triamine was reacted withacetone in a 1:1 molar ratio, only about 12% of the secondary amine wasformed. This is also true for Example 13 wherein the reactants werereacted in the molar ratio of 1:2 and Example 14 wherein a molar ratioof 1:3 was employed. However, in Example 15 when the polyoxypropylenetriamine was reacted with acetone in a 1:6 ratio, the final productcontained 84% secondary amine.

In contrast to the foregoing results, when an attempt was made to reacthydrogen with ethylenediamine and acetone in the presence of ahydrogenation catalyst in a 3:1 mole ratio under the reaction conditionsof the present invention, negative results were obtained in that therewas no detectable formation of either N,N'-diisopropyl ethylenediamineor N'-isopropyl ethylenediamine.

Use of N-(2-Butyl)Polyoxyethylene and/or Polyoxypropylene Diamines andTriamines as Epoxy Curing Agents Example 17 (6250-73-2)--Usage of 1° and2° Amine Mixtures from EDR-148/Acetone/H₂ Reactions

The mixture of N-isopropyl triethylene glycol diamine (ca. 75%) andN,N'-diisopropyl triethylene glycol diamine (ca. 25%), 15 g (6250-73-2)and EPON®828 (37 g) was mixed well and poured into a mold. After curingat ca. 70° C. for 2 hours, a flexible, transparent and tough materialwas made. The reaction was repeated except using N,N'-diisopropyltriethylene glycol diamine (11.7 g, 95% pure) and EPON 828 (18.7 g).After heating at 70° C. for a few hours, it was observed that themixture failed to cure at this temperature. After overnight curing, asoft material was obtained (transparent, plastic-like).

Example 18 (6285-11-1)--Usage of Product

The sample of 6285-11-1 containing 22% secondary amine (10 g) was mixedthoroughly with EPON®828 (Shell product, 20 g). The fluid mixture waspoured into a mold and cured at approx. 80° C. overnight. The materialwas hard, transparent polymer product.

Example 19 (6285-83-1)

The sample of 6285-83-1 containing 84% secondary amine (10 g) and EPON828 (13 g) was mixed and poured into a mold and cured at approx. 80° C.for overnight. The material was very soft, flexible at 80° C. and hardat room temperature. A thermoplastic-like unique material was obtained.

Comments

Note from Example 17 that use of the N,N'-diisopropyl triethylene glycoldiamine product of the present invention to cure a 1,2-epoxy resinresulted in the formation of a cured product which was soft andtransparent. In Example 18 wherein the product was a triamine, a hardtransparent material was obtained when the product contained only 22% ofthe secondary amine. However, in Example 19 wherein the curing agentcontained 84% secondary amine, a unique thermoplastic flexible epoxideproduct was formed.

It is seen from this that the secondary diamine and triamine reactionproducts of the present invention are excellent flexible curing agentsfor epoxy resins.

WORKING EXAMPLES--CONTINUOUS RUNS

There is a significant improvement in reaction selectivity with animproved production of the desired di- and tri-secondary isopropyl aminereaction products when the polyoxyalkylene primary diamine and triaminestarting materials of the present invention and acetone are reacted withhydrogen in the presence of a fixed bed of a pelleted hydrogenationcatalyst (preferably a nickel-containing hydrogenation catalyst, such asone containing about 60 to about 85 mole percent of nickel, about 14 toabout 37 mole percent of copper and about 1 to about 5 mole percent ofchromium, as chromia) in a continuous reactor under reaction conditionsincluding a temperature of about 100° C. to about 200° C. and a totalpressure of about 1,000 to about 4,000 psig, including a hydrogenpartial pressure of about 1,000 to about 4,000 psig, at a liquid hourlyspace velocity for the combined acetone and diamine or triamine feedcomponents of about 0.5 to about 3 w/hr/w. This is illustrated by thefollowing examples.

Example 20 (6310-88)--Continuous Reaction of Triethylene Glycol Diamine(Jeffamine EDR-148 Amine) and Acetone with Hydrogen

The experiment was performed in a 1,250 ml. tubular reactor having aninner diameter of 1.337 inches and a catalyst bed depth of 56 inches. Athermowell fabricated from 1/4 inch o.d. tubing extended upward into thecatalyst bed a distance of about 46 inches to allow temperaturemeasurements at four different points. The reactor was jacketed to allowcirculation of liquid Dowtherm for temperature control.

Jeffamine EDR-148 amine and acetone were pumped separately at rates ofabout 0.63 #/hr and 0.74 #/hr, respectively, and were combined into asingle liquid feed before entering the bottom of the reactor. Also,about 26 liters/hr of hydrogen gas (expressed at 0° C. and 1 atmosphere)were charged to the bottom of the reactor. These feed rates represent afeed mole ratio of 3.00 moles of acetone/mole of EDR-148, a spacevelocity of 0.5 g of liquid feed per hour per pound of catalyst and a100% excess of hydrogen feed, basis the acetone charge. Liquid and gasfeeds were passed upward through the catalyst bed and maintained at atemperature in the range of 133° to 150° C. Reactor effluent was cooledand passed through a back-pressure regulator set to maintain 2,500 psigpressure in the reactor. Product from the regulator was discharged intoa receiver in which the liquid product was collected at atmosphericpressure and from which gases were vented. Analysis of the liquidproduct indicated that a 100% conversion of the EDR-148 startingmaterial was obtained, giving 93% of di-secondary isopropylamine productand 4% of mono-secondary isopropyl amine product on a mole basis.

Example 20 was essentially repeated, except for changes in spacevelocity and feedstock, as noted in Table 1 with the results that arethere set forth.

                                      TABLE 1                                     __________________________________________________________________________    Continuous Phase Production of N,N'-Diisopropyl                               Polyoxyethylene and Polyoxypropylene Diamines                                             Amine/          Selectivity                                                   Acetone   Conversion                                                                          Percent                                           Notebook                                                                            Starting                                                                            Molar     Based on                                                                            di-  mono                                         Number                                                                              Amine Ratio                                                                              LSHV Amine Sec. Sec.                                         __________________________________________________________________________    6310-88                                                                             EDR-148                                                                             1:3  0.5  100   93   4                                            6340-1                                                                              EDR-148                                                                             1:3  1.0  100   88   8                                            6340-2                                                                              EDR-148                                                                             1:2.4                                                                              0.5  100   75   20                                           6340-3                                                                              EDR-148                                                                             1:2.4                                                                              1.0  100   79   18                                           6340-4                                                                              EDR-148                                                                             1:4  0.5  100   95   3                                            6340-7                                                                              EDR-192                                                                             1:3  1.0  100   90   6                                            6340-8                                                                              EDR-192                                                                             1:3  2.0  100   87   13                                           6340-13                                                                             D-230 1:3  1.0  --    64(2°)                                     6340-18                                                                             EDA   1:3  1.0  100   70   20                                           6340-19                                                                             EDA   1:4  1.0  100   92                                                __________________________________________________________________________

The foregoing examples are given by way of illustration only and are notintended as limitations on the scope of this invention as defined by theappended claims.

What is claimed is:
 1. A curable epoxy resin composition comprising:(a)a vicinal epoxy resin having an epoxide equivalency of about 0.8 toabout 1.2, and (b) a curing amount of an epoxy resin curing agentrepresented by the formula: ##STR9## wherein R is the nucleus of anoxyalkylation susceptible polyhydric alcohol containing 2 to 12 carbonatoms and 2 or 3 hydroxy groups, R' is hydrogen or methyl, at least oneof R" is isopropyl and the remainder of R" is hydrogen or isopropyl, nis a number sufficient to impart a molecular weight of about 200 to 400to the molecule, and m is a positive integer having a value of 2 or 3.2. A curable epoxy resin composition as in claim 1 wherein the curingagent has the formula: ##STR10## wherein n is a number sufficient toimpart a molecular weight of about 200 to 400 to the molecule,R'represents hydrogen or methyl, and R'"represents hydrogen or anisopropyl group.
 3. A curable epoxy resin composition as in claim 1wherein the curing agent comprises N,N'-diisopropyl triethylene glycoldiamine.
 4. A curable epoxy resin composition as in claim 1 wherein thecuring agent has the formula: ##STR11## wherein R' represents hydrogenor methyl,R'" represents 1 to 3 isopropyl groups and the remainder ofR'" is H, A represents the nucleus of an oxyalkylation-susceptibletrihydric alcohol containing 3 to 12 carbon atoms, x, y and z representnumbers, and the sum of x+y+z represents a number sufficient to impart amolecular weight of about 220 to about 400 to the molecule.
 5. A curableepoxy resin composition as in claim 4 wherein R' is methyl, A representsthe nucleus of trimethylol propane and the sum of x+y+z represents anumber sufficient to impart a molecular weight of about 400 to themolecule.
 6. A cured epoxy resin product comprising the product obtainedon curing a curable epoxy resin composition comprising:(a) a vicinalepoxy resin having an epoxide equivalency of about 0.8 to about 1.2, and(b) a curing amount of an epoxy resin curing agent represented by theformula: ##STR12## wherein at least one of R" is isopropyl and theremainder of R" is hydrogen or isopropyl, wherein R is the nucleus of anoxyalkylation susceptible polyhydric alcohol containing 2 to 12 carbonatoms and 2 or 3 hydroxy groups, R' is hydrogen or methyl, n is a numbersufficient to impart a molecular weight of about 200 to 400 to themolecule, and m is a positive integer having a value of 2 or
 3. 7. Acured epoxy resin composition as in claim 6 wherein the curing agent hasthe formula: ##STR13## wherein n is a number sufficient to impart amolecular weight of about 200 to 400 to the molecule,R' representshydrogen or methyl, and R'" represents hydrogen or an isopropyl group.8. A cured epoxy resin composition as in claim 7 wherein the curingagent comprises N,N'-diisopropyl triethylene glycol diamine.
 9. A curedepoxy resin composition as in claim 6 wherein the curing agent has theformula: ##STR14## wherein: R' represents hydrogen or methyl,R'"represents 1 to 3 isopropyl groups and the remainder of R'" is H, Arepresents the nucleus of an oxyalkylation-susceptible trihydric alcoholcontaining 3 to 12 carbon atoms, x, y and z represent numbers, and thesum of x+y+z represents a number sufficient to impart a molecular weightof about 220 to about 400 to the molecule.
 10. A cured epoxy resincomposition as in claim 9 wherein R' is methyl, A represents the nucleusof trimethylol propane and the sum of x+y+z represents a numbersufficient to impart a molecular weight of about 400 to the molecule.11. In a method of curing a vicinal epoxy resin having an epoxyequivalence of about 0.8 to 1.2 wherein a curing agent is incorporatedinto said vicinal epoxy resin and the resultant composition is heatedfor a period of time sufficient to react the curing agent with thevicinal epoxy resin and cure said resultant composition, the improvementwhich comprises using as the curing agent a compound having the formula:##STR15## wherein at least one of R"' is isopropyl and the remainder ofR"' is hydrogen or isopropyl,wherein R is the nucleus of anoxyalkylation susceptible polyhydric alcohol containing 2 to 12 carbonatoms and 2 or 3 hydroxy groups, R' is hydrogen or methyl, n is a numbersufficient to impart a molecular weight of about 200 to 400 to themolecule, and m is a positive integer having a value of 2 or
 3. 12. In amethod as in claim 11, the improvement wherein the curing agent has theformula: ##STR16## wherein n is a number sufficient to impart amolecular weight of about 200 to 400 to the molecule,R' representshydrogen or methyl, and R'" represents hydrogen or an isopropyl group.13. In a method as in claim 12, the improvement wherein the curing agentis N,N'-diisopropyltriethylene glycol diamine.
 14. In a method as inclaim 11, the improvement wherein the curing agent has the formula:##STR17## wherein: R' represents hydrogen or methyl,R'" represents 1 to3 isopropyl groups and the remainder of R'" is H, A represents thenucleus of an oxyalkylation-susceptible trihydric alcohol containing 3to 12 carbon atoms, x, y and z represent numbers, and the sum of x+y+zrepresents a number sufficient to impart a molecular weight of about 220to about 400 to the molecule.
 15. In a method as in claim 12, theimprovement wherein the curing agent is a curing agent of the formula ofclaim 13 wherein R' is methyl, A represents the nucleus of trimethylolpropane and the sum of x+y+z represents a number sufficient to impart amolecular weight of about 400 to the molecule.